Polyalklbicylic derivatives

ABSTRACT

The compound according to the formula set forth below  
                 
 
     and the use of the compound in creating fragrances, and scents in items such as perfumes, colognes and personal care products is disclosed.

FIELD OF THE INVENTION

[0001] The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancechemicals.

BACKGROUND OF THE INVENTION

[0002] U.S. Pat. Nos. 5,227,367; 5,733,866; and 5,665,698 herebyincorporated by reference as iset forth in their entirety disclosepolycyclic chemicals that are suitable for use as fragrance chemicals.Those with skill in the art appreciate how differences in the chemicalstructure of the molecule can result in significant differences in theodor, notes and characteristics of a molecule. These variations and theongoing need to discover and use the new chemicals in the development ofnew fragrances allows perfumers to apply the new compounds in creatingnew fragrances.

SUMMARY OF THE INVENTION

[0003] The present invention provides novel chemicals, and the use ofthe chemicals to enhance the fragrance of perfumes, toilet waters,colognes, personal products and the like. In addition, the presentinvention is directed to the use of the novel chemicals to enhancefragrance in perfumes, toilet waters, colognes, personal products andthe like.

[0004] More specifically, the present invention is directed to the novelcompounds, represented by the structure of Formula I set forth below:

[0005] Another embodiment of the invention is a method for enhancing afragrance by incorporating an olfactory acceptable amount of thecompound provided above.

[0006] These and other embodiments of the present invention will beapparent by reading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

[0007] The novel compounds of the present invention are more fullydescribed by the following structures:

[0008] where X, A, and B are as described above.

[0009] Those with skill in the art will appreciate that the dotted linerepresents a single or double bond. In a preferred embodiment themolecule does not contain a double bond. In a highly preferredembodiment the molecules contain the ring structure without the doublebond and m=0. These molecules are represented by the followingstructure:

[0010] where A, B and X have the definition set forth above. In apreferred embodiment of the invention the compounds have the followingstructure

[0011] Most preferably M=0 and R and R′ are independently selected fromH and CH₃.

[0012] Highly preferred embodiments of the invention are the followingcompounds wherein the substituents have the following values whenapplied to the compound of Formula I: COMPOUND A, B, X, M. VALUES4,10,10,11,12,12- A and B together (intentionally X is M = 0; and therings hexamethyl-3- form the 5 left blank) CH₃ are saturatedoxatricyclo[7.3.0.0,<2,6>] member ring dodecane structure and R is H andR′ is CH₃ 4,4,10,10,11,12,12- A and B together (intentionally X is M =0; and the rings heptamethyl-3- form the 5 left blank) CH₃ are saturatedoxatricyclo[7.3.0.0,<2,6>] member ring dodecane structure and R is CH₃and R′ is CH₃ 1,1,2,3,3-pentamethyl-5- A is = 0 B is the ketone X is M =0; and the prop-2-enyl-2,3,5,6,7- structure and R CH₃ double bond ispentahydroinden-4-one is H present 1,1,2,3,3-pentamethyl-5- A is = 0 Bis the ketone X is M = 0; and the (2-methylprop-2-enyl)- structure and RCH₃ double bond is 2,3,5,6,7- is CH₃ present pentahydroinden-4-one

[0013] The novel compounds of the present invention are prepared by oneof several reaction sequences set forth below. The compounds of Examples1, 2, 3, 8, 9, 10, 12, 13, and 14, set forth below, were prepared by thesequence:

[0014] The reaction sequence set forth above is summarized by thefollowing reactions. The first reaction is a three (3) carbon additionvia allyl alcohol Claisen rearrangement or carbon alkylation withmethallyl chloride. This reaction (Claisen rearrangement) is typicallyconducted at a temperature of from about 150 to about 250° C. In apreferred embodiment the reaction is catalyzed using an acid catalyst,preferably methanesulfonic acid or para toluenesulfonic acid. The carbonaddition reaction is then followed by an aluminum hydride ketonereduction reaction. The ketone is reduced to form the correspondingalcohol. The final reaction set forth above is an acid catalyzed etherformation that is conducted at a temperature of from about 70 to about130° C. This reaction is usually conducted in a solvent such as xyleneor toluene with toluene being the preferred solvent.

[0015] The compounds of Examples 5-7 were prepared by the followinggeneral sequence:

[0016] The first reaction is a carbon alkylation employing either allylchloride or methallyl chloride depending if the desired R group is H orCH₃. This reaction is typically conducted at a temperature of from about23 to about 100° C. The reaction is usually conducted with a basecatalyst employing sodium methoxide or sodium hydroxide. The nextreaction is a thermal Claisen rearrangement conducted at a temperatureof from about 170 to about 250° C. The third reaction is an acidcatalyzed ether formation employing similar temperatures and catalystsas described above, followed by a catalytic hydrogenation employingrhodium or platinum as a catalyst.

[0017] The compounds of Examples 4 and 11 are prepared by the sequence:

[0018] wherein the reaction is a three (3) carbon addition via allylalcohol Claisan rearrangement or carbon alkylation with methallylchloride using the conditions and catalysts described above.

[0019] The starting materials when M=0 for the above described reactioncan be found in U.S. Pat. Nos. 5,227,367, 5,733,866 and 5,665,698.Similarly, the starting materials for the above materials when M=1 canbe found in U.S. Pat. No. 3,927,083, hereby incorporated by reference,German patent 2330648 and Japanese patent 09249584.

[0020] Those with skill in the art will recognize that the compounds ofthe present invention have several chiral centers, thereby providingnumerous isomers of the claimed compounds. As used herein the compoundsdescribed herein include the isomeric mixtures of the compounds as wellas those isomers that may be separated using techniques known to thosewith skill in the art. Suitable techniques include chromatography,particlularly gel chromatography.

[0021] The optical isomers for the compound 4, 10, 10, 11, 12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane are provided in thefollowing table. One with skill in the art would be able to formulatefragrance compositions using one or more or the following isomers andmixtures of the isomers: (1R, 2R, 4R, 6R, 9R, 11R)-Z (1S, 2S, 4R, 6R,9S, 11S)-Z (1S, 2R, 4R, 6R, 9S, 11S)-Z (1R, 2R, 4R, 6R, 9R, 11S)-Z (1R,2S, 4R, 6S, 9R, 11S)-Z (1R, 2R, 4R, 6S, 9S, 11S)-Z (1R, 2R, 4R, 6R, 9S,11R)-Z (1S, 2S, 4S, 6R, 9S, 11R)-Z (1S, 2R, 4R, 6R, 9R, 11S)-Z (1R, 2R,4R, 6S, 9R, 11R)-Z (1S, 2S, 4R, 6S, 9R, 11S)-Z (1S, 2S, 4S, 6S, 9S,11S)-Z (1R, 2R, 4S, 6R, 9R, 11R)-Z (1S, 2R, 4S, 6R, 9S, 11S)-Z (1S, 2R,4S, 6S, 9R, 11S)-Z (1R, 2S, 4R, 6R, 9R, 11R)-Z (1R, 2S, 4R, 6S, 9S,11S)-Z (1S, 2S, 4R, 6R, 9R, 11S)-Z (1S, 2R, 4R, 6R, 9R, 11R)-Z (1S, 2S,4R, 6R, 9S, 11R)-Z (1S, 2S, 4S, 6R, 9R, 11R)-Z (1R, 2R, 4R, 6R, 9S,11S)-Z (1S, 2R, 4R, 6S, 9S, 11R)-Z (1S, 2S, 4R, 6S, 9S, 11R)-Z (1R, 2R,4R, 6S, 9S, 11R)-Z (1S, 2R, 4R, 6S, 9R, 11S)-Z (1R, 2R, 4S, 6S, 9S,11S)-Z (1R, 2R, 4S, 6S, 9R, 11R)-Z (1R, 2R, 4S, 6R, 9S, 11S)-Z (1S, 2R,4S, 6R, 9S, 11S)-Z (1R, 2S, 4S, 6R, 9R, 11R)-Z (1R, 2R, 4S, 6S, 9R,11S)-Z (1S, 2R, 4S, 6S, 9R, 11S)-Z (1S, 2S, 4R, 6R, 9R, 11R)-Z (1R, 2S,4R, 6R, 9S, 11R)-Z (1S, 2S, 4R, 6R, 9S, 11R)-Z (1R, 2R, 4R, 6S, 9S,11S)-Z (1R, 2S, 4R, 6S, 9R, 11R)-Z (1S, 2R, 4R, 6S, 9S, 11S)-Z (1R, 2R,4S, 6S, 9S, 11R)-Z (1R, 2R, 4S, 6R, 9R, 11S)-Z (1S, 2S, 4R, 6R, 9S,11S)-Z (1R, 2S, 4S, 6S, 9R, 11R)-Z (1R, 2S, 4R, 6R, 9S, 11R)-Z (1S, 2S,4S, 6R, 9R, 11S)-Z (1S, 2S, 4S, 6R, 9R, 11R)-Z (1R, 2R, 4S, 6S, 9R,11R)-Z (1S, 2S, 4S, 6S, 9R, 11R)-Z (1R, 2S, 4S, 6S, 9S, 11R)-Z (1S, 2R,4S, 6R, 9S, 11R)-Z (1R, 2S, 4S, 6S, 9S, 11S)-Z (1R, 2R, 4R, 6S, 9R,11S)-Z (1S, 2S, 4S, 6S, 9S, 11R)-Z (1S, 2S, 4R, 6S, 9R, 11R)-Z (1R, 2R,4S, 6R, 9S, 11R)-Z (1S, 2S, 4S, 6S, 9R, 11S)-Z (1R, 2S, 4S, 6R, 9S,11R)-Z (1R, 2S, 4R, 6S, 9R, 11R)-Z (1S, 2S, 4S, 6R, 9S, 11S)-Z (1R, 2S,4S, 6R, 9R, 11S)-Z (1S, 2R, 4S, 6R, 9R, 11R)-Z (1S, 2S, 4R, 6S, 9S,11S)-Z (1S, 2R, 4S, 6S, 9S, 11S)-Z (1R, 2R, 4S, 6S, 9R, 11S)-Z

[0022] The compounds of the present invention have a powerful amberfragrance, with soft, woody notes.

[0023] The use of the compounds of the present invention is widelyapplicable in current perfumery products, including the preparation ofperfumes and colognes, the perfuming of personal care products such assoaps, shower gels, and hair care products as well as air fresheners andcosmetic preparations. The present invention can also be used to perfumecleaning agents, such as, but not limited to detergents, dishwashingmaterials, scrubbing compositions, window cleaners and the like.

[0024] In these preparations, the compounds of the present invention canbe used alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

[0025] Many types of fragrances can be employed in the presentinvention, the only limitation being the compatibility with the othercomponents being employed. Suitable fragrances include but are notlimited to fruits such as almond, apple, cherry, grape, pear, pineapple,orange, strawberry, raspberry; musk, flower scents such aslavender-like, rose-like, iris-like, carnation-like. Other pleasantscents include herbal and woodland scents derived from pine, spruce andother forest smells. Fragrances may also be derived from various oils,such as essential oils, or from plant materials such as peppermint,spearmint and the like.

[0026] A list of suitable fragrances is provided in U.S. Pat. No.4,534,891, the contents of which are incorporated by reference as if setforth in its entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

[0027] Olfactory effective amount is understood to mean the amount ofcompound in perfume compositions the individual component willcontribute to its particular olfactory characteristics, but theolfactory effect of the perfume composition will be the sum of theeffects of each of the perfumes or fragrance ingredients. Thus thecompounds of the invention can be used to alter the aromacharacteristics of the perfume composition, or by modifying theolfactory reaction contributed by another ingredient in the composition.The amount will vary depending on many factors including otheringredients, their relative amounts and the effect that is desired.

[0028] The level of compound of the invention employed in the fragrancedarticle varies from about 0.005 to about 10 weight percent, preferablyfrom about 0.5 to about 8 and most preferably from about 1 to about 7weight percent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

[0029] Another method of reporting the level of the compounds of theinvention in the perfumed composition, i.e., the compounds as a weightpercentage of the materials added to impart the desired fragrance. Thecompounds of the invention can range widely from 0.005 to about 70weight percent of the perfumed composition, preferably from about 0.1 toabout 50 and most preferably from about 0.2 to about 25 weight percent.Those with skill in the art will be able to employ the desired level ofthe compounds of the invention to provide the desired fragrance andintensity.

[0030] The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to meanparts per million; mm is understood to be millimeters, ml is understoodto be milliliters, Bp is understood to be boiling point, THF isunderstood to be tetrahydrofuran, Hg is understood to be mercury and gis understood to be grams. IFF as used in the examples is understood tomean International Flavors & Fragrances Inc., Hazlet, N.J., USA.

EXAMPLE 1

[0031] Preparation of7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one

[0032] The synthesis of the starting material for this example is setforth in U.S. Pat. Nos. 5,227,367, 5,733,866, 5,665,698.

[0033] A 3 liter flask equipped with a vigreux column and a distillationhead was charged with 624 g (3 mole) of7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 435 g (7.5 mole) allylalcohol, 97 g (1.6 mole) acetic acid, and 15 g (0.16 mole)methanesulfonic acid. The mixture was heated to 80-85° C. Trimethylorthoformate 350 g (3.3 mole) was added over 24 hours with removal oflights (methanol) atmospherically. The reaction mass was heated to 180°C. with removal of lights and aged at 180° C. for 2 hr. The crudereaction mass was cooled and 800 ml of water and 400 ml of toluene wasadded. The aqueous layer was discarded and the organic layer was washedwith brine.

[0034] The crude organic layer was distilled to recover toluene as wellas 285 g of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-oneas a mixture of isomers (Bp 106° C. at 1 mmHg).

[0035] The nmr spectrum of7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one is asfollows: 0.68-1.13 ppm (ms, 15H), 1.34-1.63 ppm (m, 5H), 1.77-2.50 ppm(m, 4H), 4.93 ppm (m, 2H), 5.74 ppm (m, 1H)

EXAMPLE 2

[0036] Preparation of7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol

[0037] A mixture of VITRIDE® (Zeeland Chemicals) 70% in toluene, 338 g(1.17 mole) and toluene (732 ml) was heated to 100° C.7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-one, 290 g(1.17 mole) was added over 2 hrs. The excess VITRIDE® was neutralizedwith 2-propanol (105 g) and the reaction mass was quenched with aqueoussodium hydroxide (280 g of 50% NaOH). The lower aqueous layer wasdiscarded and the organic layer was washed with brine.

[0038] The organic layer was distilled to recover toluene, as well as163 g of 7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol asa mixture of isomers (Bp 128-130° at 3 mmHg).

[0039] The nmr spectrum of7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol is asfollows: 0-59-1.02 ppm (ms, 15H), 1.14-1.58 ppm (m, 5H), 1.66-2.53 ppm(m, 4H), 3.25-3.87 ppm (dd, 1H), 3.93-4.05 ppm (bs, 1H), 4.98-5.11 ppm(m, 2H), 5.70-5.94 ppm (m, 1H).

EXAMPLE 3

[0040] Preparation of4.10.10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane

[0041] A mixture of7,7,8,9,9-pentamethyl-3-prop-2-enylbicyclo[4.3.0]nonan-2-ol, 163 g (0.65mole), toluene 163 g and methanesulfonic acid 11.5 g (0.11 mole) washeated to 80-90° C. The reaction mass was aged for 24 hours then cooledto room temperature. The reaction was quenched with 10% aqueous sodiumcarbonate solution (50 ml). The organic layer was washed twice with 10%aqueous sodium carbonate solution (50 ml) then brine.

[0042] The organic layer was distilled to recover toluene as well as 112g of 4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane asa mixture of isomers (Bp 95° C. at 2 mm Hg).

[0043] The nmr spectrum of4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane is asfollows: 0.63-0.96 ppm (ms, 18H), 1.0-2.15 ppm (m, 9H), 3.94-4.28 ppm(m, 2H).

EXAMPLE 4

[0044] Preparation of1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7-pentahydroinden 4-one

[0045] A mixture of CASHMERAN® (IFF) 1000 g (4.85 mole), allyl alcohol1245 g (21.46 mole), and methanesulfonic acid (MSA) 50 g (0.52 mole) washeated to 80-90° C. Volatile organic materials were collected for 24hrs. The MSA was neutralized 25% sodium methoxide solution in methanol(142 g) and the reaction mass was heated to 180° C. for 5 hours. Themixture was cooled and toluene 1000 milliliters was added. The crudemass was washed twice with brine.

[0046] The organic layer was distilled to recover toluene, CASHMERAN®(IFF) (490 g), and 205 g of1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7-pentahydroinden-4-one (Bp139-141° C. at 7 mm Hg).

[0047] The nmr spectrum of1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7-pentahydroinden-4-one wasas follows: 0.87-1.22 ppm (ms, 15H), 1.56-1.78 ppm (m, 2H), 1.99-2.38ppm (m, 3H), 2.55-2.68 ppm (m, 1H), 5.02-5.11 ppm (m,2H), 5.72-5.88 ppm(m,1H).

EXAMPLE 5

[0048] Preparation of 5-(allyloxy)-1,1,2,3,3-pentamethyl indane

[0049] The synthesis of the starting material for this example is setforth in U.S. Pat. Nos. 5,227,367, 5,733,866, 5,665,698.

[0050] A mixture of 1,1,2,3,3-pentamethyl-4-indanol, 195 g (0.95 mole),methanol (880 ml), sodium iodide, 0.32 g (0.002 mole), and 25% sodiummethoxide solution in methanol, 395 g (1.82 mole) was stirred and heatedto 40° C. Allyl chloride 151 g (1.96 mole) was added dropwise over 3hours. The reaction mixture was aged 24 hours at 40° C. The reaction wascooled to room temperature and diluted with 2 liters of water. The pHwas adjusted with 100 ml of concentrated hydrochloride acid (37%hydrochloric acid). Toluene (390 ml) was added and the lower aqueouslayer was discarded. The organic layer was washed with 300 ml of 10%aqueous sodium carbonate solution then twice with brine.

[0051] The organic layer was distilled to recover toluene as well as 122g of 5-(allyloxy)-1,1,2,3,3-pentamethyl indane (Bp 134-137C at 8.7 mmHg).

[0052] The nmr spectrum of 5-(allyloxy)-1,1,2,3,3-pentamethyl indane wasas follows: 0.96-1.41 ppm (ms, 15H), 1.83 ppm (q, 1H), 4.49 ppm (dd,2H), 5.18-5.42 ppm (m, 2H), 5.95-6.08 ppm (m, 1H), 6.52 ppm (d, 1H),6.67 ppm (d, 1H), 7.00 ppm (t, 1H).

EXAMPLE 6

[0053] Preparation of 1,1,2,3,3-pentamethyl-5-prop-2-enylindan-4-ol

[0054] 5-(Allyloxy)-1,1,2,3,3-pentamethyl indane, 122 g (0.5 mole) andPRIMOL (Exxon) 36 g was heated to 180-200° C. for 12 hrs.

[0055] The reaction mass was distilled providing 38 g of1,1,2,3,3-pentamethyl-5-prop-2-enylindan-4-ol (Bp 152-154° C. at 5mmHg).

[0056] The nmr spectrum of 1,1,2,3,3-pentamethyl-5-prop-2-enylindan-4-olwas as follows: 0.961.42 ppm (ms, 15H), 1.87 ppm (q, 1H), 3.39 ppm (bd,2H), 5.02 ppm (bs,1H), 5.16-5.27 ppm (m,2H), 5.98-6.10 ppm (m, 1H), 6.70ppm (d, 1H), 6.95 ppm (d, 1H).

EXAMPLE 7

[0057] Preparation of2,6,6,7,8,8-hexamethyl-2,3-dihydroindano[4,5-b]furan

[0058] A mixture of 1,1,2,3,3-pentamethyl-5-prop-2-enylindan-4-ol 38 g(0.15 mole), toluene 100 ml and p-toluenesulfonic acid (ptsa) 2.3 g(0.01 mole) was heated to 80-90° C. for 15 hours. The reaction mass wascooled to room temperature and quenched with 10% aqueous sodiumcarbonate (100 ml). The aqueous layer was discarded and organic layerwas washed once with brine.

[0059] The organic layer was distilled to recover toluene as well as2,6,6,7,8,8-hexamethyl-2,3-dihydroindano[4,5-b]furan (Bp 124° C. at 4 mmHg).

[0060] The nmr spectrum of2,6,6,7,8,8-hexamethyl-2,3-dihydroindano[4,5-b]furan was as follows:1.21-1.68 ppm (ms, 18H), 2.07 ppm (q, 1H), 2.92 ppm (ddd, 1H), 3.41 ppm(ddd, 1H), 5.01-5.16 ppm (m, 1H), 6.75 ppm (d,1H), 7.07 ppm (d,1H).

EXAMPLE 8

[0061] Preparation of7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one

[0062] Lithium diisopropylamide 1L (2.0 M in THF) was cooled to −10° C.7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 320 g (1.50 mole) wasadded dropwise over 2 hrs. The reaction mass was aged 2 hours at roomtemperature then hexamethylphosporamide available from AldrichChemicals, (HMPA), 5.37 g (2 mole %), sodium iodide, 4.50 g (2 mole %)and methallyl chloride, 150 g (1.60 mole) were added over 2 hrs. Thereaction mass was heated to reflux for 8 hours. The mixture was cooledto room temperature and quenched with water, 450 g. The aqueous layerwas separated then discarded. The organic layer was washed with brine.

[0063] The organic layer was distilled to recover THF as well as 384 gof7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one(Bp 110° C. at 2 mm Hg).

[0064] The nmr spectrum of7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-oneis as follows: 0.68-1.25 ppm (ms,15H), 1.30-1.87 ppm (m, 6H), 2.03-2.18ppm (m, 2H), 2.61 ppm (bd, 1H), 4.58-4.73 ppm (m, 2H).

EXAMPLE 9

[0065] Preparation of7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol

[0066]7,7,8,9,9-Pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-one,140 g (0.53 mole) in toluene (60 g) was fed into RED-AL® (available fromAldrich Chemicals) (65% in toluene) 231 g (0.74 mole) at roomtemperature over 3 hrs. The reaction mass was quenched with aqueouscaustic soda (147 g of 20% NaOH). The mass was heated to 65° C. thenwater (500 ml) was added. The aqueous layer was separated and extractedonce with toluene (86 g). The combined organic layers were dried oversodium sulfate.

[0067] The organic layer was distilled to recover toluene as well as7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol asa mixture of isomers (Bp 132-133° C. at 3 mm Hg).

[0068] The nmr spectrum of7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol isas follows: 0.61-1.02 ppm (ms, 15H), 1.05-1.56 ppm (m, 6H), 1.71-1.88ppm (m,4H), 1.95-2.54 ppm (m,2H), 3.25-3.96 ppm (m,1H), 4.67-4.80 ppm(m, 2H).

EXAMPLE 10

[0069] Preparation of 4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0<2.6>]dodecane

[0070] A solution of7,7,8,9,9-pentamethyl-3-(2-methylprop-2-enyl)bicyclo[4.3.0]nonan-2-ol,2.31 g (8.8 millimole), methanesulfonic acid, 0.04 g (0.4 millimole),and 1-nitropropane 2.31 g was stirred for 24 hrs at room temperature.The reaction mass was neutralized with aqueous sodium carbonate (10%solution). The aqueous layer was separated and discarded. The organiclayer was concentrated on a rotary evaporator.

[0071] Distillation provided4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0<2,6>]-dodecane as amixture of isomers (Bp 98° C. at 2 mm Hg).

[0072] The nmr spectrum of4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane wasas follows: 0.61-1.27 ppm (ms, 21H), 1.32-1.85 ppm (m, 6H), 2.45-2.61ppm (m, 1H) 3.92-3.98 ppm (m, 1H).

EXAMPLE 11

[0073] Preparation of1,1,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)-2,3,5,6,7-pentahydroinden-4-one

[0074] A solution of CASHMERAN® (IFF) 400 g (1.94 mole) and THF (200milliliter) was fed into lithium diisopropylamide 1L (2.0 M in THF) at−10° C. The reaction mass was aged for 2 hours and allowed to warm to 0°C. Methallyl chloride 248 g (2.7 mole) was added over 2 hours. Thereaction was warmed to room temperature, then heated to 60° C. for 20hours. The mixture was cooled and quenched with 10% hydrochloric acid (1liter). The crude mass was washed with brine.

[0075] The organic layer was distilled to recover THF and 310 g of1,1,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)-2,3,5,6,7-pentahydroinden-4-one(Bp 142-143° C. at 2 mm Hg).

[0076] The nmr spectrum of1,1,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)-2,3,5,6,7-pentahydroinden-4-oneis as follows: 0.86-1.23 ppm (ms,15H), 1.36-1.66 ppm (m, 2H), 1.72 ppm(bs, 3H), 1.75-2.39 ppm (m, 4H), 2.59-2.71 ppm (m,1H), 4.70 ppm (d, 2H).

EXAMPLE 12

[0077] Preparation of3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one

[0078] A solution of 7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one 200g (0.97 mole) and THF (100 mL) is fed into lithium diisopropylamide 1L(1.0 M in THF) and HMPA (10 g 5 mole percent at −30° C. The reactionmass is aged for 2 hours and allowed to warm to 0° C. 1,2-Dibromoethane200 g (1.06 mole) is added over 2 hours. The reaction is warmed to roomtemperature and aged for 24 hrs. The mixture is quenched with 10%hydrochloric acid (200 mL). The crude mass is washed with brine.

[0079] Distillation would provide3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one as amixture of isomers.

EXAMPLE 13

[0080] Preparation of3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-ol

[0081] A solution of3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-one, 200 g(0.63 mole) in toluene (60 g) is fed into RED-AL® (65% in toluene) 218 g(0.70 mole) at 60° C. in 1 hr. The reaction mass is quenched withaqueous caustic soda (200 g of 50% NaOH) at 60° C. The mass is dilutedwith water (500 ml) and cooled to room temperature. The aqueous layer isseparated and discarded.

[0082] Distillation would provide3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-ol as amixture of isomers.

EXAMPLE 14

[0083] Preparation of10,10,11,12,12-pentamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane

[0084] A solution of3-(2-bromoethyl)-7,7,8,9,9-pentamethylbicyclo[4.3.0]nonan-2-ol, 50 g(0.16 mole) and THF (100 ml) is fed into sodium hydride 6.4 g (60%dispersion in mineral oil) and THF (300 ml) at room temperature. Thereaction mass is heated to reflux for 8 hours and cooled to roomtemperature. The reaction mass is quenched with brine (100 ml). Theaqueous layer is separated and discarded.

[0085] Distillation would provide10,10,11,12,12-pentamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane as amixture of isomers.

EXAMPLE 15

[0086] A fragrance was prepared according to the following formulation:Materials Parts4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane 1BORNAFIX ® (IFF) 3 CEDRAFIX ® (IFF) 2.5 CELESTOLIDE ® (IFF) 4 CITRALVA ®(IFF) 1 Citrus oil distilled 12 CYCLACET ® (IFF) 3 CYCLOGALBANIFF ®(IFF) 1 Dihydro Myrcenol 40 FLEURANIL ® (IFF) 1 Geranium Bourbon Oliffac0.5 Hexyl Cinnamic Aldehyde 4.5 ISO E SUPER ® (IFF) 2.5 KHARISMAL ®(IFF) 2 KOAVONE ® (IFF) 1.5 Linalyl Acetate 5 PHENOXANOL ® (IFF) 3PRECYCLEMONE B ® (IFF) 1.5 Pseudo Linalyl Acetate 5 Styralyl Acetate 1VIGOFLOR ® 1 ZENOLIDE ® (IFF) 4

[0087] This fragrance was described as having a citrus odor.

EXAMPLE 16

[0088] The following materials made in the above examples were describedas having the following fragrance characteristics: Material Odor4,10,10,11,12,12-hexamethyl-3- Amber, Woodyoxatricyclo[7.3.0.0<2,6>]dodecane 4,4,10,10,11,12,12-heptamethyl-3-Amber, Woody oxatricyclo[7.3.0.0<2,6>]dodecane1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7- Sweet, Musky,pentahydroinden-4-one Fruity1,1,2,3,3-pentamethyl-5-(2-methylprop-2-enyl)- Sweet, Raspberry,2,3,5,6,7-pentahydroinden-4-one Musky

What is claimed is:
 1. The compound according to the structure:


2. The compound of claim 1 which is incorporated into a fragranceformulation.
 3. A method for improving, enhancing or modifying the odorproperties of a fragrance by incorporating an olfactory acceptableamount of the compound of claim
 1. 4. The method of claim 3 wherein thefragrance is incorporated into a product selected from perfumes,colognes, toilet waters, personal care products, cleaning products andair fresheners.
 5. The method of claim 4 wherein the cleaning product isselected from the group consisting of detergents, dishwashingcompositions, scrubbing compounds and window cleaners.
 6. The method ofclaim 5 wherein the product is a personal care product.
 7. The compoundsaccording to the structure:


8. The compound of claim 7 wherein A and B together form a ringstructure to provide a compound with the structure:


9. A method for improving, enhancing or modifying the odor properties ofa fragrance by incorporating an olfactory acceptable amount of thecompound of claim
 8. 10. The method of claim 9 wherein the compound isselected from the group consisting of4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane,4,4,10,10,11,12,12-heptamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane,1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7-pentahydroinden-4-one and1,1,2,3,3-pentamethyl-5-prop-2-enyl-2,3,5,6,7-pentahydroinden-4-one. 11.The optical isomers of compound 4, 10, 10, 11, 12,12-hexamethyl-3-oxatricyclo[7.3.0.0<2,6>]dodecane of claim 10: (1R, 2R,4R, 6R, 9R, 11R)-Z, (1S, 2S, 4R, 6R, 9S, 11S)-Z, (1S, 2R, 4R, 6R, 9S,11S)-Z, (1R, 2R, 4R, 6R, 9R, 11S)-Z, (1R, 2S, 4R, 6S, 9R, 11S)-Z, (1R,2R, 4R, 6S, 9S, 11S)-Z, (1R, 2R, 4R, 6R, 9S, 11R)-Z, (1S, 2S, 4S, 6R,9S, 11R)-Z, (1S, 2R, 4R, 6R, 9R, 11S)-Z, (1R, 2R, 4R, 6S, 9R, 11R)-Z,(1S, 2S, 4R, 6S, 9R, 11S)-Z, (1S, 2S, 4S, 6S, 9S, 11S)-Z, (1R, 2R, 4S,6R, 9R, 11R)-Z, (1S, 2R, 4S, 6R, 9S, 11S)-Z, (1S, 2R, 4S, 6S, 9R,11S)-Z, (1R, 2S, 4R, 6R, 9R, 11R)-Z, (1R, 2S, 4R, 6S, 9S, 11S)-Z, (1S,2S, 4R, 6R, 9R, 11S)-Z, (1S, 2R, 4R, 6R, 9R, 11R)-Z, (1S, 2S, 4R, 6R,9S, 11R)-Z, (1S, 2S, 4S, 6R, 9R, 11R)-Z, (1R, 2R, 4R, 6R, 9S, 11S)-Z,(1S, 2R, 4R, 6S, 9S, 11R)-Z, (1S, 2S, 4R, 6S, 9S, 11R)-Z, (1R, 2R, 4R,6S, 9S, 11R)-Z, (1S, 2R, 4R, 6S, 9R, 11S)-Z, (1R, 2R, 4S, 6S, 9S,11S)-Z, (1R, 2R, 4S, 6S, 9R, 11R)-Z, (1R, 2R, 4S, 6R, 9S, 11S)-Z, (1S,2R, 4S, 6R, 9S, 11S)-Z, (1R, 2S, 4S, 6R, 9R, 11R)-Z, (1R, 2R, 4S, 6S,9R, 11S)-Z, (1S, 2R, 4S, 6S, 9R, 11S)-Z, (1S, 2S, 4R, 6R, 9R, 11R)-Z,(1R, 2S, 4R, 6R, 9S, 11R)-Z, (1S, 2S, 4R, 6R, 9S, 11R)-Z, (1R, 2R, 4R,6S, 9S, 11S)-Z, (1R, 2S, 4R, 6S, 9R, 11R)-Z, (1S, 2R, 4R, 6S, 9S,11S)-Z, (1R, 2R, 4S, 6S, 9S, 111R)-Z, (1R, 2R, 4S, 6R, 9R, 11S)-Z, (1S,2S, 4R, 6R, 9S, 11S)-Z, (1R, 2S, 4S, 6S, 9R, 11R)-Z, (1R, 2S, 4R, 6R,9S, 11R)-Z, (1S, 2S, 4S, 6R, 9R, 11S)-Z, (1S, 2S, 4S, 6R, 9R, 11R)-Z,(1R, 2R, 4S, 6S, 9R, 11R)-Z, (1S, 2S, 4S, 6S, 9R, 11R)-Z, (1R, 2S, 4S,6S, 9S, 11R)-Z, (1S, 2R, 4S, 6R, 9S, 11R)-Z, (1R, 2S, 4S, 6S, 9S,11S)-Z, (1R, 2R, 4R, 6S, 9R, 11S)-Z, (1S, 2S, 4S, 6S, 9S, 11R)-Z, (1S,2S, 4R, 6S, 9R, 11R)-Z, (1R, 2R, 4S, 6R, 9S, 11R)-Z, (1S, 2S, 4S, 6S,9R, 11S)-Z, (1R, 2S, 4S, 6R, 9S, 11R)-Z, (1R, 2S, 4R, 6S, 9R, 11R)-Z,(1S, 2S, 4S, 6R, 9S, 11S)-Z, (1R, 2S, 4S, 6R, 9R, 11S)-Z, (1S, 2R, 4S,6R, 9R, 11R)-Z, (1S, 2S, 4R, 6S, 9S, 11S)-Z, (1S, 2R, 4S, 6S, 9S,11S)-Z, (1R, 2R, 4S, 6S, 9R, 11S)-Z.